Abstract: A method of forming a microelectronic structure on a substrate is disclosed. The method includes applying an underlayer forming composition to an uppermost intermediate layer of a lithography stack, if present, or to the substrate to form an underlayer. The underlayer forming composition includes a pre-ionic compound that generates an ionic compound, moiety, or both during post-application bake. The pre-ionic compound can include, for example, a copolymer having glycidyl methacrylate and 4-vinylpyridine. An EUV-sensitive photoresist comprising a metal-oxide is applied directly on an upper surface of the underlayer. EUV lithography is then performed. This method can be used to achieve dose reduction compared to prior art methods of EUV lithography using metal-oxide containing photoresists. Various underlayer forming compositions for performing EUV lithography using a metal-oxide-containing resist are also disclosed.

Abstract: Adhesive additives are disclosed that enhance spin-on carbon (SOC) resistance to SC-1 wet etch. The additives can be formed by reacting a polymer or oligomer (such as an adhesion polymer or adhesion oligomer) with 3,4,5-triacetoxybenzoic acid (TABA). When added to standard SOC layers or used as a primer between an SOC layer and substrate, these additives enhance the adhesion of the SOC layer to TiN and other substrates and reduce undercut during SC-1 wet etch.

Abstract: Materials and methods are described for filling deep trenches and other topography using a single coating of a topographic fill material and a single develop back step while maintaining a thickness that can be controlled and is sufficient to fill very deep topographies to the extent needed for lithographic patterning. The materials are designed for selective changes to their solubility, and the methods involve using this feature to achieve selective removal of desired amounts of the topographic fill material at various stages of the process. This allows more efficient processing and higher throughput for lithographic applications in which a photoresist is applied over deep topography while addressing the problems of resist cracking, bending, peeling, or scumming.

Abstract: Methods of using an acid-generating, spin-on carbon (SOC) layer for EUV lithography are disclosed. The methods can be used to reduce the dose, scumming, and/or nanobridges induced by insufficient acid at the bottom of a photoresist for both line/space (LS) and contact hole (CH) applications. The methods may improve uniformity in acid compensation at the bottom of the photoresist via bottom-up diffusion of an acid from the acid-generating layer. By utilizing the acid-generating SOC layer under a spin-on silicon hardmask or spin-on glass (SOG), dose reduction has been realized.

Abstract: Compositions and methods for global planarization of microelectronic substrates are provided. The methods include applying a crosslinking modifier composition to the surface of a substrate, or to any intermediate layer(s) on the substrate surface. A planarizing material can then be applied to the crosslinking modifier layer, which influences the degree of crosslinking in the planarizing layer. Depending on the specific topography of the underlying substrate (or intermediate layer), different amounts of planarizing material are removed during a subsequent develop back step, thereby eliminating bias that usually exists between regions of varying topographic density. The result is an effective global planarization method that is both time and cost efficient.

Abstract: A novel method to prepare crosslinked thin films without the use of catalysts is disclosed. Propiolic acid is grafted to a glycidyl or epoxy group using a phosphonium catalyst under mild conditions to yield a propiolate ester. The propiolate ester is thermally crosslinkable (and the polymer film rendered insoluble) at temperatures as low as 120° C., and some embodiments may undergo photoinduced crosslinking upon exposure to DUV light. The resulting crosslinked films are equivalent or better in stability to acid-catalyzed epoxide crosslinked films and can be used for a multitude of different applications.

Abstract: Methods for direct patterning of a silicon hardmask with extreme ultraviolet (EUV) radiation are provided. The method involves forming a polysiloxane and/or oligosiloxane composition into a silicon hardmask layer followed by solvent removal. Without using a photoresist and/or other layer silicon hardmask layer, condensation of the siloxane sol-gel polymers and/or oligomers is induced by EUV radiation, rendering the exposed portions insoluble in typical lithography solvents or developers. The exposed portions of the silicon hardmask layer are removed, leaving a pattern in the silicon hardmask layer that can be transferred to any layers below the silicon hardmask layer, and ultimately to the substrate.

Abstract: Thermally decomposable gap-fill materials are disclosed that fill small features and are completely removed by a high-temperature bake after processing. These materials are self-crosslinkable polymers. Potential applications of these materials include use as sacrificial gap-fill materials for creating air gaps, as well as protection of high-aspect-ratio or other delicate microelectronic features during processing steps.

Abstract: Adhesive additives are disclosed that enhance spin-on carbon (SOC) resistance to SC-1 wet etch. The additives can be formed by reacting a polymer or oligomer (such as an adhesion polymer or adhesion oligomer) with 3,4,5-triacetoxybenzoic acid (TABA). When added to standard SOC layers or used as a primer between an SOC layer and substrate, these additives enhance the adhesion of the SOC layer to TiN and other substrates and reduce undercut during SC-1 wet etch.

Abstract: Novel block copolymers (“BCPs”) having non-random distributions of comonomers within at least one of the blocks and methods of using those BCPs in directed self-assembly (“DSA”) processes are provided. The non-random (e.g., gradient-creating) distributions can be customized in order to concentrate the desired comonomer properties in predetermined areas of the BCP. These BCPs can achieve perpendicular orientation with simple annealing and offer superior long-range ordering and lower defectivity when compared to prior art BCPs. These BCPs can be incorporated into compositions that simultaneously offer the benefits of high-? and rapid thermal-annealing kinetics while maintaining similar or improved guide process windows when compared to prior art BCPs.

Abstract: Block copolymers for use in block copolymer lithography, self-assembled films of the block copolymers and methods for polymerizing the block copolymers are provided. The block copolymers are characterized by high Flory-Huggins interaction parameters (?). The block copolymers can be polymerized from protected hydroxystyrene monomers or from tert-butyl styrene and 2-vinylpyridine monomers.

Abstract: Crosslinkable random copolymers comprising atom transfer radical polymerization (ATRP) initiators and crosslinked copolymer films formed from the copolymers are provided. The random copolymers, which are polymerized from one or more alkyl halide functional inimers and one or more monomers having a crosslinkable functionality, are characterized by pendant ATRP initiating groups and pendant crosslinkable groups.

Abstract: Novel block copolymers (“BCPs”) having non-random distributions of comonomers within at least one of the blocks and methods of using those BCPs in directed self-assembly (“DSA”) processes are provided. The non-random (e.g., gradient-creating) distributions can be customized in order to concentrate the desired comonomer properties in predetermined areas of the BCP. These BCPs can achieve perpendicular orientation with simple annealing and offer superior long-range ordering and lower defectivity when compared to prior art BCPs. These BCPs can be incorporated into compositions that simultaneously offer the benefits of high-? and rapid thermal-annealing kinetics while maintaining similar or improved guide process windows when compared to prior art BCPs.

Abstract: Crosslinkable random copolymers comprising atom transfer radical polymerization (ATRP) initiators and crosslinked copolymer films formed from the copolymers are provided. The random copolymers, which are polymerized from one or more alkyl halide functional inimers and one or more monomers having a crosslinkable functionality, are characterized by pendant ATRP initiating groups and pendant crosslinkable groups.

Abstract: Block copolymers for use in block copolymer lithography, self-assembled films of the block copolymers and methods for polymerizing the block copolymers are provided. The block copolymers are characterized by high Flory-Huggins interaction parameters (?). The block copolymers can be polymerized from protected hydroxystyrene monomers or from tert-butyl styrene and 2-vinylpyridine monomers.

Abstract: Block copolymers for use in block copolymer lithography, self-assembled films of the block copolymers and methods for polymerizing the block copolymers are provided. The block copolymers are characterized by high Flory-Huggins interaction parameters (?). The block copolymers can be polymerized from protected hydroxystyrene monomers or from tert-butyl styrene and 2-vinylpyridine monomers.

Abstract: Block copolymer-based mask structures for the growth of patterned polymer brushes via surface-initiated atom transfer radical polymerization (SI-ATRP) are provided. Also provided are methods of making the mask structures and methods of using the mask structures to grow patterned polymer brushes. The mask structures comprise a substrate having a surface, a neutral layer comprising a crosslinked copolymer film disposed on the surface of the substrate and a domain-forming block copolymer film disposed on the crosslinked copolymer film. The crosslinked copolymer film comprises crosslinked random copolymer chains having pendant alkyl halide functional groups that are capable of acting as ATRP initiating sites.

Abstract: Block copolymers for use in block copolymer lithography, self-assembled films of the block copolymers and methods for polymerizing the block copolymers are provided. The block copolymers are characterized by high Flory-Huggins interaction parameters (?). The block copolymers can be polymerized from protected hydroxystyrene monomers or from tert-butyl styrene and 2-vinylpyridine monomers.

Abstract: Polymer films comprising crosslinked random copolymers and methods for making the films are provided. Also provided are polymer films comprising random copolymers that are covalently linked to an underlying substrate. The polymer films can be incorporated into structures in which the films are employed as surface-modifying layers for domain-forming block copolymers and the structures can be used for pattern transfer applications via block copolymer lithography. The crosslinks between the random copolymer chains in the polymer films or the links between the random copolymer chains and the substrate surface are characterized in that they can be cleaved under relatively mild conditions.